Method and apparatus for reducing nitrous oxide

ABSTRACT

A process and a device for reducing the nitrous oxide which is formed during the catalytic combustion of ammonia and oxygen to form nitrogen oxides is provided, where a catalyst system consisting of at least one first catalyst mesh element and at least one second catalyst mesh element is used for the catalytic combustion of ammonia and oxygen to form nitrogen oxides, where the minimum of one first catalyst mesh element consists of platinum-rhodium mesh and the minimum of one second, downstream catalyst mesh element consists of palladium-rhodium mesh with 2-4 wt. % of rhodium.

[0001] The invent-on pertains to a process and to a device for reducing the nitrous oxide which is formed during the catalytic combustion of ammonia and oxygen to form nitrogen oxides, where a catalyst system consisting of at least one first catalyst mesh element and at least a second catalyst mesh element is used for the catalytic combustion of ammonia and oxygen to form nitrogen oxides, and where at least one first catalyst mesh element is a platinum-rhodium mesh element.

[0002] A familiar problem in the production of nitric acid by the combustion of ammonia with oxygen to form suitable nitrogen oxides is the fact that nitrous oxide (laughing gas) is also formed, which is under suspicion of contributing to the destruction of the earth's ozone layer. In the production of nitric acid, therefore, it is extremely important to effectively destroy the N₂O which has formed or to prevent nitrous oxide from being formed as completely as possible in the first place. The attempt to achieve these ends should not impair the yield of the desired nitrogen oxides.

[0003] DE 198-19,882 A1 discloses a process for the catalytic decomposition of the N₂O present in a gas mixture obtained during the production of nitric acid by the catalytic oxidation of ammonia. This process makes use of a catalyst for the decomposition of N₂O and is characterized in that the hot gas mixture obtained from the catalytic oxidation of ammonia is brought into contact with the N₂O-decomposing catalyst before the mixture is cooled.

[0004] DE-OS 2,239,514 discloses an arrangement of catalyst gauze strips for accelerating the reaction between two or more gases flowing through the gauze, which is characterized in that, or the downward-directed flow side of a group of gauze strips of precious metal material, a second group of gauze strips consisting of non-precious metal material, relatively difficult-to-vaporize metal material, and metal material which can be carried away by the gases is provided, which second groups supports the acceleration of the reaction during the operation of the system.

[0005] DE-OS 1,959,137 discloses a catalyst with a reduced platinum and rhodium content of 12-20 wt. % for the oxidation of ammonia to nitrogen oxide.

[0006] In Hollemann-Wiberg, Lehrbuch der anorganischen Chemie [Textbook of Organic Chemistry], 71-b 80 ^(th) edition, Verlag Walter de Gruyter & Co., Berlin, 1971, p. 360, an ammonia combustion element for recovering nitrogen oxide with a platinum mesh catalyst and larger systems with several stacked wire mesh elements per combustion element are described.

[0007] EP 0,359,286 B1 describes a process for reducing the nitrous oxide which is formed during the catalytic combustion of ammonia and oxygen to form nitrogen oxides. The nitrous oxide is cooled in a heat recovery unit and then absorbed in water and/or dilute nitric acid. The process is characterized in that the hot combustion gases are given a retention time of 0.1-3 seconds before they are cooled. In this way, it is possible to decompose up to 90% of the N₂O which has formed.

[0008] EP 0,611,041 B1 discloses a process for reducing the N₂O emissions during the startup phase of an ammonia oxidation reaction. A catalyst mesh based on platinum is used together with a platinum collector mesh element, which comprises fibers of a palladium alloy, said palladium alloy containing 0.1-5 wt. % of cobalt.

[0009] DE 198-G5,202 A1 describes a process for the production of nitric acid in which ammonia is burned on at least one catalyst mesh element, especially on a platinum mesh element, as oxygen is being supplied. The reaction gases are then cooled. Before the reaction gases are cooled downstream of the catalyst mesh, they are conducted over a heat-resistant catalyst to convert the N₂O contained in the reaction gases.

[0010] The processes indicated above either have unsatisfactory N₂O decomposition rates or require a very complicated apparatus, which must be considered disadvantageous in an economic sense.

[0011] The problem is therefore to find a novel method and a novel device for reducing nitrous oxide while avoiding at least some of the disadvantages listed above and especially to provide an efficient process and a corresponding device which are low in cost in terms of the required apparatus.

[0012] This problem is solved according to the invention by a process according to Claim 1 or Claim 2, by a device according to Claim 6 or Claim 7, and by a use according to Claim 11.

[0013] Both in the process according to the invention and in the corresponding device according to the invention, ammonia is mixed with oxygen and burned at a temperature of approximately 860° C by passing it quickly over a first catalyst mesh element, which consists of platinum-rnodium mesh typically containing 5.0-10.0 wt. % of rhodium, and then by passing it quickly over a second catalyst mesh element, this second catalyst consisting of palladium-rhodium mesh with at least 92 wt. % (or more) of palladium, 2-4 wt. % of rhodium, and the remainder of platinum or alternatively of 82-83 wt. % of pallacium, 2.5-3.5 wt. % of rhodium, and the remainder of platinum, as a result of which the proportion of nitrous oxide is reduced in a highly efficient manner. The mesh used here is a gas-permeable structure which is essentially metallic and which is produced by, for example, knotting, knitting, weaving, or the random laying of fibers.

[0014] The surprising result was obtained that, through the simultaneous use of the two catalyst mesh elements according to the invention, the proportion of N₂O that forms could be decreased significantly right from the start, and simultaneously NO could be produced in a highly efficient manner.

[0015] It is advantageous, first, for the palladium-rhodium mesh to have a rhodium content of 2.5-3 wt. % and a palladium content of 82.5%, because in this way an especially low level of N₂O formation can be reached.

[0016] It is also advantageous for the palladium-rhodium mesh element to be separated from the platinum-rhodium mesh element by least one third mesh element, so that in this way it is possible to prevent the different types of mesh elements from becoming welded together. As material for the third mesh element, a heat-resisting steel (FeCrAl alloy, e.g., Megapyr or Kanthal) has been found to give good results.

[0017] Finally, it can be advantageous for the palladium-rhodium mesh to contain an additional metal from the group consisting of iridium, ruthenium, rhenium, cobalt, nickel, copper, and gold to increase the mechanical stability of the palladium-rhodium catalyst mesh elements without interfering with their catalytic function.

[0018] The following examples are presented to explain the invention in greater detail.

[0019] 1. Experiments in the Test Reactor System Data: reactor: test reactor with an effective diameter of 100 mm; reactor pressure: 5 bars; load: 10 tN/m²day; temperature: 865° C.; running time: 20 days. Example 1 (Standard System) PtRh8 meshes + PdNi5 meshes Selectivity of conversion 95.5-96% from ammonia to nitrogen oxide: N₂O output: 1,000-1,200 ppm Example 2 (Comparison Example) PtRh8 meshes + PdRh1.5 meshes Selectivity of conversion 95.5-96% from ammonia to nitrogen oxide: N₂O output: 1,000-1,200 ppm Example 3 (Comparison Example) PtRh8 meshes + PdRh5 meshes Selectivity of conversion 94.5-95% from ammonia to nitrogen oxide: N₂O output: 900-1,200 ppm Example 4 (Invention) PtRh8 meshes + PdRh3 meshes Selectivity of conversion 95.5-96% from ammonia to nitrogen oxide: N₂O output: 300-500 ppm Remark: Pd meshes mechanically very weak after use. Cracks were present. Example 5 (Invention) PtRh8 meshes + PdRh3Pt5 meshes Selectivity of conversion 95.5-96% from ammonia to nitrogen oxide: N₂O output: 300-500 ppm Remark: Pd meshes mechanically very weak after use, but no cracks present. Example 6 (Invention) PtRh8 meshes + PdRh3Pt15 meshes Selectivity of conversion 95.5-96% from ammonia to nitrogen oxide: N₂O output: 300-500 ppm Remark: Pd meshes mechanically stable after use, but no cracks present.

[0020] 2.1. Experiments in the Industrial Reactor System Data: reactor: industrial system with two parallel reactors; reactor pressure: 4.8 bars; load: 11.2 tN/m²day; temperature: 880° C.; running time: 180 days. Reactor 1 (Standard System) PtRh5 meshes + PdNi5 meshes Converstion of ammonia 95% To nitrogen oxide: N₂O output: 1,500 ppm Reactor 2 (Invention) PtRh5 meshes + PdPt15Rh2.5 meshes Conversion of ammonia 95% To nitrogen oxide: N₂O output: 1,000 ppm

[0021] 2.2. Experiments in the Industrial Reactor System Data: reactor: industrial reactor; reactor pressure: 3.5 bars; load: 5.85 tN/m²day; temperature: 860° C.; run time: 300 days. Example 1 (Standard System) PtRh5 meshes + PdNi5 meshes Converstion of ammonia 94-96% To nitrogen oxide: N₂O output: 1,200-1,600 ppm Example 2 (Invention) PtRh5 meshes + PdPt15Rh3 meshes Conversion of ammonia 94-96% To nitrogen oxide: N₂O output: 400-800 ppm 

1. Process for reducing the nitrous oxide which is formed during the catalytic combustion of ammonia and oxygen to form nitrogen oxides, where a catalyst system consisting of at least one first catalyst mesh element and at least one second catalyst mesh element is used for the catalytic combustion of ammonia and oxygen to form nitrogen oxides, and where the minimum of one first catalyst mesh element consists of platinum-rhodium mesh, characterized in that at least one second, downstream catalyst mesh element consists of palladium-rhodium mesh with at least 92 wt. % of palladium, 2-4 wt. % of rhodium, and the remainder of platinum.
 2. Process for reducing the nitrous oxide which is formed during the catalytic combustion of ammonia and oxygen to form nitrogen oxides, where a catalyst system consisting of at least one first catalyst mesh element and at least one second catalyst mesh element is used for the catalytic combustion of ammonia and oxygen to form nitrogen oxides, and where the minimum of one first catalyst mesh element consists of platinum-rhodium mesh, characterized in that the minimum of one second, downstream catalyst mesh element consists of palladium-rhodium mesh with 82-83 wt. % of palladium, 2.5-3.5 wt. % of rhodium, and the remainder of platinum.
 3. Process according to claim 2, characterized in that the palladium-rhodium mesh has a rhodium content of 2.5-3 wt. % and a palladium content of 82.5 wt. %.
 4. Process according to one of claims 1-3, characterized in that the palladium-rhodium mesh element is separated from the platinum-rhodium mesh element by at least one third mesh element.
 5. Process according to claim 4, characterized in that the third mesh element consists of a heat-resisting steel.
 6. Device or reducing the nitrous oxide which is formed during the catalytic combustion of ammonia and nitrogen to form nitrogen oxides, where a catalyst system consisting of at least one first catalyst mesh element and at least one second catalyst mesh element is used for the catalytic combustion of ammonia and oxygen to form nitrogen oxides, and where the minimum of one first catalyst mesh element consists of platinum-rhodium mesh, characterized in that the second, downstream catalyst mesh element consists of palladium-rhodium mesh with at least 92 wt. % of palladium, 2-4 wt. % of rhodium, and the remainder of platinum.
 7. Device for reducing the nitrous oxide which is obtained during the catalytic combustion of ammonia and oxygen to form nitrogen oxides, where a catalyst system consisting of at least one first catalyst mesh element and at least one second catalyst mesh element is used for the catalytic combustion of ammonia and oxygen to form nitrogen oxides, and where the minimum of one first catalyst mesh element consists of platinum-rhodium mesh, characterized in that the second, downstream catalyst mesh element consists of palladium-rhodium mesh with 82-83 wt. % palladium, 2.5-3.5 wt. % rhodium, and the remainder of platinum.
 8. Device according to claim 7, characterized in that the palladium-rhodium mesh has a rhodium content of 2.5-3 wt. % and a palladium content of 82.5 wt. %.
 9. Device according to one of claims 6-8, characterized in that the palladium-rhodium mesh element is separated from the platinum-rhodium mesh element by at least one third mesh element.
 10. Device according to one of claims 6-9, charaterized in that the third mesh element consists of a heat-resisting steel.
 11. Use of a device according to one of claims 6-10 to reduce nitrous oxide, especially the nitrous oxide that forms during the catalytic combustion of ammonia and oxygen to form nitrogen oxides. 